I don't want to disappoint or discourage anyone but I feel that I have to point out some simple facts about DotNetNuke skinning.
To put it straightaway, when we talk about DotNetNuke skinning we talk about a pretty simple process with a pretty quick learning curve. But the point is that a DNN skin is not just some special tags and content panes. To design and then develop a DNN skin means that you know at least the basics about web design. How to produce optimized graphics using photoshop or any other graphics software, how to code an HTML page and how to apply CSS styles, is essential knowledge someone who wants to create a skin must have. Even further, when someone wants to produce professional and high quality skins, have to be a professional and skilled web designer.
So, before start thinking about how to create your own custom DotNetNuke skin, be sure to ask yourself about your web design skills. If you don't do that, you'll end up thinking that a custom DotNetNuke skin is a very painful process which is not true... not at all.